Publications

Abstract Carbon dots (CDs) are carbon-based nanomaterials with advantageous luminescent properties, making them promising alternatives to other molecular and nanosized fluorophores. However, the development of CDs is impaired by the low synthesis yield of standard fabrication strategies, making high-yield strategies essential. To help future studies to focus on cleaner production strategies, we have employed a Life Cycle Assessment (LCA) to compare and understand the environmental impacts of available routes for the high-yield synthesis of carbon dots. These routes were: (1) production of hydrochar, via hydrothermal treatment of carbon precursors, and its alkaline-peroxide treatment into high-yield carbon dots; (2) thermal treatment of carbon precursors mixed in a eutectic mixture of salts. Results show that the first synthesis route is associated with the lowest environmental impacts. This is attributed to the absence of the mixture of salts in the first synthesis route, which offsets its higher electricity consumption. Sensitivity analysis showed that the most critical parameter in the different synthetic strategies is the identity of the carbon precursor, with electricity being also relevant for the first synthesis route. Nevertheless, the use of some carbon precursors (as citric acid) with higher associated environmental impacts may be justified by their beneficial role in increasing the luminescent performance of carbon dots. Thus, the first synthesis route is indicated to be the most environmental benign and should be used as a basis in future studies aimed to the cleaner and high-yield production of carbon dots.

Abstract Dioxetanone is one of the prototypical cyclic peroxide intermediates in several chemiluminescent and bioluminescent systems, in which thermolysis reactions allow efficient singlet chemiexcitation. While the chemiexcitation mechanism of dioxetanone and peroxide intermediates is still far from understood, the presence of a peroxide bond that undergoes bond breaking has been found to be a constant. Here we have addressed the following questions: can other non-peroxide bonds lead to chemiexcitation and, if not, can the differences between dioxetanone and non-peroxide derivatives help to elucidate their chemiexcitation mechanism? To this end, we have used a reliable TD-DFT approach to model the thermolysis and chemiexcitation of a model dioxetanone and its three other non-peroxide derivatives. The results showed that only the dioxetanone molecule could lead to chemiluminescence as it is the only one for which thermolysis is energetically favorable and provides a pathway for singlet chemiexcitation. Finally, the chemiexcitation of the model dioxetanone is explained by its access, during thermolysis, to a biradical region where the ground and excited states are degenerate. This occurs due to an increased interaction between the reaction fragments, which extends the biradical regions and delays the rupture of the peroxide ring.

Abstract <jats:p>The present work reports an experimental thermodynamic study of two nitrogen heterocyclic organic compounds, fenclorim and clopyralid, that have been used as herbicides. The sublimation vapor pressures of fenclorim (4,6-dichloro-2-phenylpyrimidine) and of clopyralid (3,6-dichloro-2-pyridinecarboxylic acid) were measured, at different temperatures, using a Knudsen mass-loss effusion technique. The vapor pressures of both crystalline and liquid (including supercooled liquid) phases of fenclorim were also determined using a static method based on capacitance diaphragm manometers. The experimental results enabled accurate determination of the standard molar enthalpies, entropies and Gibbs energies of sublimation for both compounds and of vaporization for fenclorim, allowing a phase diagram representation of the (p,T) results, in the neighborhood of the triple point of this compound. The temperatures and molar enthalpies of fusion of the two compounds studied were determined using differential scanning calorimetry. The standard isobaric molar heat capacities of the two crystalline compounds were determined at 298.15 K, using drop calorimetry. The gas phase thermodynamic properties of the two compounds were estimated through ab initio calculations, at the G3(MP2)//B3LYP level, and their thermodynamic stability was evaluated in the gaseous and crystalline phases, considering the calculated values of the standard Gibbs energies of formation, at 298.15 K.</jats:p>

Abstract The aim of the present study was to investigate the eco-cytotoxicity of several forms of nanomaterials (NM), such as nano-CuO, nano-TiO2, nano-SiO2 and nano-ZnO, on different aquatic species (Raphidocelis subcapitata, Daphnia magna and Lemna minor) following standard protocols and on human cell lines (Caco-2, SV-80, HepG2 and HaCaT). Predicted no-effect concentrations (PNEC) or hazard concentrations for 5% of the species (HC5) were also estimated based on the compilation of data available in the literature. Most of the NM agglomerated strongly in the selected culture media. For the ecotoxicity assays, nano-CuO and nano-ZnO even in particle agglomeration state were the most toxic NM to the freshwater organisms compared to nano-TiO2 and nano-SiO2. Nano-ZnO was the most toxic NM to R. subcapitata and D. magna, while nano-CuO was found to be very toxic to L. minor. Nano-CuO was very toxic to Caco-2 and HepG2 cells, particularly at the highest tested concentrations, while the other NM showed no toxicity to the different cell lines. The HC5 and PNEC values are still highly protective, due to data limitations. However, the present study provides consistent evidence of the potential risks of both nano-CuO and nano-ZnO against aquatic organisms and also their effects on public health.

Abstract Photodynamic therapy (PDT) is an anticancer therapeutic modality with remarkable advantages over more conventional approaches. However, PDT is greatly limited by its dependence on external light sources. Given this, PDT would benefit from new systems capable of a light-free and intracellular photodynamic effect. Herein, we evaluated the heavy-atom effect as a strategy to provide anticancer activity to derivatives of coelenterazine, a chemiluminescent single-molecule widespread in marine organisms. Our results indicate that the use of the heavy-atom effect allows these molecules to generate readily available triplet states in a chemiluminescent reaction triggered by a cancer marker. Cytotoxicity assays in different cancer cell lines showed a heavy-atom-dependent anticancer activity, which increased in the substituent order of hydroxyl < chlorine < bromine. Furthermore, it was found that the magnitude of this anticancer activity is also dependent on the tumor type, being more relevant toward breast and prostate cancer. The compounds also showed moderate activity toward neuroblastoma, while showing limited activity toward colon cancer. In conclusion, the present results indicate that the application of the heavy-atom effect to marine coelenterazine could be a promising approach for the future development of new and optimized self-activating and tumor-selective sensitizers for light-free PDT.

Abstract Osteoporosis therapies leveraging bisphosphonates and mineral components (e.g., magnesium, calcium, and strontium) have been raising attention because of their potential for managing this ever-growing disease. The administration of multicomponent therapeutics (combined therapy) in elderly patients is complex and suffers from low patient adherence. Herein, we report an all-in-one combination of four antiosteoporotic components into a new family of coordination complexes: [M-2(H(4)alen)(4)(H2O)(2)]center dot 1.5H(2)O [where M2+ = Mg2+ (1), (Mg0.535Ca0.465)(2+) (2) and (Mg0.505Ca0.450Sr0.045)(2+) (3)]. These solid-state complexes were prepared, for the first time, through microwave-assisted synthesis. It is demonstrated that the compounds are capable of releasing their antiosteoporotic components, both in conditions that mimic the path along the gastrointestinal tract and in long periods under physiological conditions (pH similar to 7.4). More importantly, when administered in low concentrations, the compounds did not elicit a cytotoxic effect toward liver, kidney, and osteoblast-like cell lines. Besides, it is important to highlight the unique coordination complex with four bone therapeutic components, [(Mg0.505Ca0.450Sr0.045)(2)(H(4)alen)(4)(H2O)(2)]center dot 1.5H(2)O (3), which significantly promoted osteoblast metabolic activity up to ca. 1.4-fold versus the control group. These findings bring this type of compounds one-step closer to be considered as an all-in-one and more effective treatment for managing chronic bone diseases, prompting further research on their therapeutic properties.

Abstract <jats:p>Carbon dots (CDs) are fluorescence carbon-based nanomaterials that possess several properties such as photoluminescence, biocompatibility and good water solubility. They can be fabricated from a large variety of precursors; however, most available organic molecules are still expensive and their use or synthesis can lead to significant challenges to the environment and human health. It has become desirable to use biomass waste as alternative precursors in the synthesis of CDs, given that biomass waste material is ubiquitous, nontoxic, cheap and renewable. Spent coffee grounds (SCGs) are the residues of the treatment of coffee powder can be a potential carbon source to a more environmentally sustainable synthesis route. In this work, we fabricated SCG-based CDs via one-pot and solvent-free carbonization at 200 °C of solid samples generating particles with sizes between 2.1 and 3.9 nm. These carbon nanoparticles exhibited blue fluorescence and excitation-dependent emission of carbon dots with moderate quantum yields (2.9–5.8%). The presence of heavy metals in water resources, such as Fe3+, can lead to adverse health effects. SCG-based CDs showed potential for being used as optical Fe3+ optical sensors, with Life Cycle Assessment (LCA) studies validating the SCGs as more sustainable precursors than classical precursors, both considering a weight- or function-based functional unit.</jats:p>

Abstract Ionic liquids (ILs) are remarkable chemical compounds with applications in many areas of modern science. They are increasingly recognized as promising compounds to fight microorganisms in both planktonic and biofilm states, contributing to reinvent the antimicrobial pipeline. Biofilm-related infections are particularly challenging given that the scientific community has not yet identified a reliable control strategy. Understanding of the action of ILs in biofilm control is is still in a very early stage. However, given the highly tunable nature and exceptional properties of ILs, they are excellent candidates for biofilm control. Here, we review the major advances in, and challenges tothe use of ILs for effective biofilm control.

Abstract Computer-aided design of new drugs is an exponentially growing field, especially in the last decade. The support of theoretical tools may accelerate the drug discovery process, which is a long and very expensive journey. Tools as QSAR and docking calculations are on the top of the list for helping medicinal chemists to find more potent and selective molecules as potential leads for facing challenging diseases. Coumarins have been an important source of inspiration for the design of new drugs. Due to their chemical properties and their affinity to some targets, special attention has been paid to their role against neurodegenerative diseases. Therefore, the authors provide an overview of the scientific reports describing the research and development of new drug design tools supporting the discovery of coumarins as enzymatic inhibitors or receptor ligands involved in these diseases. This review emphasizes the rationale behind the design of new drug candidates, and particular attention is paid to the search for new leads over the last 10 years. QSAR and docking studies are discussed, as well as new technologies applied for the research in this field. The manuscripts discussed in this review have been collected from multiple electronic databases, including Pubmed, SciFinder, and Mendeley.

Abstract Here we report the rational development of a carbon dot (CDs)-based fluorescent pH nanosensor by employing an active surface preservation strategy. More specifically, citric acid, urea and fluorescein were subjected to a one-pot hydrothermal treatment, which preserved fluorescein-like structures on the surface of the CDs. The obtained CDs showed pH-sensitive green emission, which can be used to determine pH variations from 3.7 to 12.1 by fluorescence enhancement. Moreover, the obtained nanoparticles showed excellent selectivity toward pH, fluorescence reversibility in different pH values, photostability, while being compatible with human cell lines (even at high concentrations). Furthermore, their performance as pH sensors was comparable with reference pH determination procedures. Thus, an active surface preservation strategy was successfully employed to develop fluorescence pH nanosensors in a rational manner and without post-synthesis functionalization strategies, which show potential for future use in pH determination.